KR102595053B1 - Insulating film deposition method, insulating film deposition device, and substrate processing system - Google Patents

Abstract

The aim is to provide a technique for obtaining good film quality in forming an insulating film containing silicon oxide as a coating film on a substrate. A coating liquid containing polysilazane is applied to the wafer W, the solvent in the coating liquid is volatilized, and then, before performing a cure process, the coating film is irradiated with ultraviolet rays in a nitrogen atmosphere. For this reason, unbonded hands are likely to be generated at hydrolyzed sites in polysilazane. Therefore, the efficiency of generating hydroxyl groups increases in that unbonded hands are created in silicon, which is a site that is hydrolyzed in advance. In other words, since the energy required for hydrolysis is reduced, even when the temperature of the cure process is set to 350°C, the remaining portions that are not hydrolyzed decrease. As a result, dehydration condensation occurs efficiently, and the crosslinking rate is improved, making it possible to form a dense (high-quality) insulating film.

Description

Insulating film deposition method, insulating film deposition device, and substrate processing system

The present invention relates to a technology for forming an insulating film that is a coating film containing silicon oxide on a substrate and is hardened from a crosslinking reaction.

During the manufacturing process of a semiconductor device, there is a process of forming an insulating film such as a silicon oxide film, and the insulating film is formed by, for example, plasma CVD or application of a coating liquid. An insulating film formed by plasma CVD has the advantage of producing a dense, high-quality film, but has poor embedding properties. Therefore, for example, it is not suitable for burying insulating material in a narrow groove called STI (shallow trench isolation), so it is necessary to repeat plasma CVD and etch back to gradually bury it so that no gap is formed. The film forming process becomes complicated, or large-scale equipment is required to perform vacuum processing.

In addition, for example, the method of applying a coating liquid to a semiconductor wafer (hereinafter referred to as "wafer") by spin coating, etc., curing the coating film, and forming an insulating film has good embedding properties, and the insulating film can be filled even in narrow patterns such as STI. easy to do. Additionally, although there is an advantage that the treatment can be performed in a normal pressure atmosphere, there is a problem in that the strength of the film is relatively low. For this reason, the strength of the film is increased by heat treating (curing) the coating film at, for example, 600°C to 800°C.

However, with the miniaturization of patterns, there is a request to suppress the thermal history of the semiconductor device being manufactured as low as possible, for example, when forming an interlayer insulating film, from the viewpoint of migration of copper (Cu) wiring, diffusion of Cu, etc. The temperature cannot be higher than 450℃. Therefore, the method of forming an insulating film by applying a coating liquid cannot be applied to an interlayer insulating film because the cure temperature is high.

Patent Document 1 describes a technique for forming an insulating film by heating the coating film at a low temperature after application of the coating film and then processing it at a high temperature in a water vapor atmosphere, but it does not solve the problem of the present invention.

Japanese Patent Publication No. 2012-174717

The present invention was made under these circumstances, and its purpose is to provide a technique for obtaining good film quality when forming an insulating film containing silicon oxide as a coating film on a substrate.

The method for forming an insulating film of the present invention includes the steps of forming a coating film by applying a coating liquid obtained by dissolving a precursor for forming an insulating film containing silicon oxide in a solvent to a substrate;

A solvent volatilization step of volatilizing the solvent in the coating film,

After this process, an energy supply process of supplying energy to the coating film in a low-oxygen atmosphere with a lower oxygen concentration than the atmosphere in order to generate unbonded losses in the molecular groups constituting the precursor;

Afterwards, the curing process includes heating the substrate and crosslinking the precursor to form an insulating film.

The insulating film forming apparatus of the present invention includes a coating module for forming a coating film by applying a coating liquid obtained by dissolving a precursor for forming an insulating film containing silicon oxide in a solvent to a substrate;

A solvent volatilization module for volatilizing the solvent in the coating film,

In order to activate the precursor, an energy supply module for supplying energy to the coating film in which the solvent has been volatilized in a low-oxygen atmosphere with a lower oxygen concentration than the atmosphere;

a cure module for heating the substrate processed in the energy supply module and crosslinking the precursor to form an insulating film;

It is characterized by being provided with a substrate transport mechanism for transporting the substrate between each module.

The substrate processing system of the present invention includes a loading and unloading port for loading and unloading a substrate into a transfer container, and a coating solution for forming a coating film by applying a coating solution in which a precursor for forming an insulating film containing silicon oxide is dissolved in a solvent to the substrate. An application module, a solvent volatilization module for volatilizing the solvent in the coating film, and an energy supply for supplying energy to the coating film in which the solvent has been volatilized in a hypoxic atmosphere with a lower oxygen concentration than the atmosphere in order to activate the precursor. A substrate processing device including modules and a substrate transport mechanism for transporting substrates between each module and the loading/unloading port;

a cure device for heating the substrate processed in the energy supply module and crosslinking the precursor to form an insulating film;

A container transport mechanism is provided for transporting the transport container between the loading/unloading port of the substrate processing apparatus and the curing device.

In the present invention, a coating liquid containing a precursor of an insulating film containing silicon oxide is applied to a substrate, the solvent of the coating liquid is volatilized, and energy is supplied to the coating film in a low-oxygen atmosphere before performing a cure process. . For this reason, unbonded hands are likely to be generated at the hydrolyzed site in the precursor. In the cure process, first, through hydrolysis, a hydroxyl group is bonded to the silicon of the molecular group constituting the precursor, and then the hydroxyl group of the molecular group is dehydrated and condensed to perform crosslinking, but unbonded losses are formed in the silicon, which is the site to be hydrolyzed in advance. Since it is being produced, the production efficiency of hydroxyl groups increases. In other words, since the energy required for hydrolysis is reduced, the remaining portions that are not hydrolyzed are reduced even if the cure process is performed at a low temperature. As a result, dehydration condensation occurs efficiently, so the crosslinking rate is improved and the production of a dense (good quality) insulating film can be expected.

1 is an explanatory diagram explaining the curing process of a conventional insulating film.
Figure 2 is an explanatory diagram explaining the curing process of the insulating film of the present invention.
3 is an explanatory diagram explaining the insulating film forming process according to the embodiment of the present invention.
FIG. 4 is an explanatory diagram explaining the insulating film forming process according to the embodiment of the present invention.
FIG. 5 is an explanatory diagram illustrating the insulating film forming process according to the embodiment of the present invention.
FIG. 6 is an explanatory diagram illustrating the insulating film forming process according to the embodiment of the present invention.
7 is an explanatory diagram explaining the insulating film forming process according to the embodiment of the present invention.
Figure 8 is an explanatory diagram explaining the reaction path of polysilazane in a conventional film forming process.
Figure 9 is an explanatory diagram explaining the reaction path of polysilazane in the film forming method of the present invention.
Fig. 10 is an explanatory diagram showing planarization of the surface of the insulating film.
Fig. 11 is a plan view showing an insulating film forming apparatus.
Fig. 12 is a vertical cross-sectional view of the insulating film forming apparatus.
FIG. 13 is a cross-sectional view showing an application module provided in the film forming system.
FIG. 14 is a cross-sectional view showing a solvent volatilization module provided in the film forming system.
FIG. 15 is a cross-sectional view showing an ultraviolet irradiation module provided in the film forming system.
FIG. 16 is a cross-sectional view showing a cure processing module provided in the film forming system.
Figure 17 is a plan view showing a substrate processing system according to an embodiment of the present invention.
FIG. 18 is an explanatory diagram illustrating the insulating film forming process according to another example of the embodiment of the present invention.
Fig. 19 is an explanatory diagram explaining the insulating film forming process according to another example of the embodiment of the present invention.
Fig. 20 is an explanatory diagram explaining the insulating film forming process according to another example of the embodiment of the present invention.
FIG. 21 is an explanatory diagram illustrating the insulating film forming process according to another example of the embodiment of the present invention.
Fig. 22 is an explanatory diagram explaining the insulating film forming process according to another example of the embodiment of the present invention.
Fig. 23 is an explanatory diagram explaining the insulating film forming process according to another example of the embodiment of the present invention.
Figure 24 is a cross-sectional view showing the surface structure of a wafer according to another example of the embodiment of the present invention.

[Summary of invention]

Before explaining the details of embodiments of the present invention, an outline of the present invention will be explained. As an example of the method of forming an insulating film of the present invention, a coating liquid containing a precursor of an insulating film containing silicon oxide is applied to a substrate, the obtained coating film is heated to volatilize the solvent in the coating film, and then the substrate is heated to form a coating film. A step of rearranging the molecular groups within the coating film, then irradiating the coating film with ultraviolet rays, and then curing the coating film can be mentioned.

The coating liquid is produced by dissolving a group of oligomers, which are the molecular group of the precursor of the insulating film containing silicon oxide, in a solvent, which is a solvent. In a general cure process, by heating the substrate to, for example, 500°C, the Si-H bond of the oligomer hydrolyzes (reacts) with H ₂ O (moisture) as shown in FIG. 1 to produce Si-OH. , dehydration condensation (reaction) continues to occur, Si-O-Si bonds are created, and the oligomers are cross-linked.

The reason why oligomers are used as components of the coating liquid is that if the entire precursor is linked, it does not dissolve in the solvent. For this reason, the state of the oligomer, that is, the state before hydrolysis of the precursor already described, is stabilized, and hydrolysis is a process that transitions from this stable state to an unstable state. Therefore, it is difficult to promote hydrolysis, and it is difficult to increase the cure temperature or Alternatively, it may be necessary to react at low temperature for a long time.

Meanwhile, the dehydration condensation reaction progresses quickly simply by applying heat energy. For this reason, if the cure temperature is raised to promote hydrolysis, dehydration condensation occurs (Si-OH becomes Si-O-Si) rather than hydrolysis (Si-H becomes Si-OH). Because this is easy, the density of the insulating film decreases. As for the reason, to put it roughly, when some oligomers are cross-linked by dehydration condensation, other oligomers may not have been hydrolyzed yet, and the other oligomers are introduced into the cross-linked product of some of the oligomers. It is presumed that it is due to what has become. Additionally, the method of curing at a low temperature for a long time reduces the throughput, making it difficult to accept on the production line.

Therefore, in the present invention, before performing the cure process, for example, ultraviolet rays are irradiated to the coating film to generate unbonded hands at the site where hydrolysis occurs (so-called activation of the oligomer). That is, as shown in FIG. 2, the energy of ultraviolet rays cleaves Si-H bonds in the oligomer to generate unbonded hands. For this reason, the energy required for hydrolysis in the cure process is lowered, so the generation efficiency of hydroxyl groups (OH groups) is increased, and the crosslinking rate by subsequent dehydration condensation is improved. This means that even if the cure process is performed at a low temperature, a dense (good film quality) insulating film can be obtained.

It is necessary to irradiate the coating film with ultraviolet rays before the curing process. The reason for this is that although the cure process is performed at a low temperature, for example, it is carried out in a heating atmosphere of 350°C to 450°C, so when unbonded losses are generated by the energy of ultraviolet rays as already explained, unbonded losses are generated. Crosslinking occurs from the site where the Si-H bond has not yet been cleaved, and as a result, oligomers whose Si-H bonds have not yet been cleaved are trapped in the group of crosslinked oligomers, lowering the density of the insulating film.

For this reason, the step of irradiating ultraviolet rays to the coating film must be performed at a temperature where this phenomenon is suppressed. Specifically, for example, 350°C or lower is considered preferable, and can be performed at room temperature, for example. In addition, the process of irradiating ultraviolet rays to the coating film needs to be performed in a low-oxygen atmosphere with an oxygen concentration lower than that of an atmospheric atmosphere, for example, in an atmosphere with an oxygen concentration of 400 ppm or less, preferably 50 ppm or less. An example of the low oxygen concentration atmosphere may be an inert gas atmosphere such as nitrogen gas.

If the oxygen concentration is high in the atmosphere in which this process is performed, oligomers with unbonded hands generated by irradiation of ultraviolet rays instantly bond to each other, and isolated oligomers are trapped within the bonded oligomers, resulting in a decrease in the density of the insulating film. .

[Embodiment]

Next, embodiments of the insulating film forming method of the present invention will be described in detail. In this example, the process of performing STI on a substrate to be processed will be explained. As shown in FIG. 3, a groove portion (trench) 110 is formed in the silicon film 100 on the wafer W, which is the substrate to be processed, and a coating solution in which a precursor of the SOG film is dissolved in an organic solvent is applied to the wafer W. ), the coating film 101 is formed to fill the trench 110. As a precursor, for example, polysilazane, a polymer whose basic structure is -(SiH ₂ NH)-, is used. In the coating liquid, for example, the molecular groups of polysilazane are dissolved in an oligomer state to improve fluidity. Therefore, as shown in FIG. 3, when the coating liquid is applied to the wafer W by, for example, spin coating, it is easy for the coating liquid to enter the narrow trench 110, and a coating film 101 with good embedding properties is obtained. 3 to 10, the coating film 101 is described as PSZ (polysilazane).

Subsequently, as shown in FIG. 4, the wafer W is heated at 100 to 250°C, for example, 150°C for 3 minutes. As a result, the solvent contained in the coating film 101 volatilizes. Next, as shown in FIG. 5, the wafer W is heated at 200 to 300°C, for example, 250°C. At this time, the oligomer contained in the coating film 101 is activated by heat. Therefore, the oligomers in the coating film 101 are rearranged and arranged to fill the gap (reflow process). By performing this reflow process, the oligomers are rearranged, thereby narrowing the gap between oligomers. Therefore, when crosslinks between oligomers are formed through the later curing treatment, it becomes easy to form a dense film.

Thereafter, as shown in FIG. 6, in an atmosphere with an oxygen concentration of 400 ppm, preferably 50 ppm or less, for example, a nitrogen (N ₂ ) gas atmosphere, 5000 mJ/cm 2 or less, for example, 4000 mJ, is applied to the coating film 101. Investigate the energy of /㎠. As energy, for example, ultraviolet rays with a main wavelength of 200 nm or less, for example, ultraviolet rays (UV) with a main wavelength of 172 nm are irradiated. The main wavelength refers to the wavelength corresponding to the maximum peak or its vicinity in the spectrum. In the subsequent cure process, as shown in FIG. 7, while supplying water vapor toward the wafer W, stepwise heat treatment is performed at a temperature of 350 to 450° C., for example, water vapor is heated to 400° C. and 450° C. under an atmosphere. Heating is carried out stepwise and further at 450°C in an N ₂ gas atmosphere.

Figure 8 shows the reaction path when curing treatment is performed on polysilazane without irradiation of ultraviolet rays, and Figure 9 shows the reaction path when curing treatment is performed on polysilazane irradiated with ultraviolet rays. As shown in FIG. 8, when polysilazane is cured, H bonded to Si becomes an OH group due to hydrolysis, and the NH group is oxidized to ammonia (NH ₃ ), forming a Si-O bond. is formed Then, a crosslink is formed through dehydration condensation between the OH groups. However, as explained in the outline of the invention, when curing is performed, hydrolysis is difficult to occur, resulting in a film with low density.

In contrast, when the coating film 101 containing polysilazane is irradiated with ultraviolet rays before curing, as shown in FIG. 9, Si-H bonds are cleaved to form unbonded hands, and some Si-N bonds are formed. This is cut to form an unpaired hand. As a result, when the cure treatment is performed, the OH group is easily bonded to the unbonded hand, and Si-OH is generated. Additionally, OH groups are cross-linked through dehydration condensation to form a Si-O-Si bond. Additionally, the Si-N bond in polysilazane is replaced by O, resulting in the production of silicon oxide. As already explained, by forming unbonded hands in advance, the OH group generation efficiency is high and the crosslinking rate is improved, so that an insulating film (silicon oxide film) of good film quality is formed.

After the insulating film is cured, as shown in FIG. 10, the excess coating film 101 on the surface of the wafer W is removed by, for example, CMP (Chemical Mechanical Polishing). At this time, if the strength of the coating film 101 is low, polishing by CMP becomes difficult, but since the coating film 101 is made of a highly dense silicon oxide film and the strength is sufficiently high, it is polished by CMP and the wafer is polished. The silicon film 100 is exposed on the surface of (W).

Next, an insulating film forming apparatus for performing the above-described insulating film forming method will be described. As shown in FIGS. 11 and 12, the insulating film deposition apparatus includes a carrier block S1, which is a port for loading and unloading wafers W into and out of the device from a carrier C, which is a transfer container containing a plurality of wafers W, and a relay block S2. It is composed of processing blocks S3 connected in series.

The carrier block S1 includes a stage 11 on which a plurality (for example, three) of carriers C for storing and transporting a plurality of wafers W are stacked, for example, in the horizontal direction (X direction), and a stage A transfer mechanism 12, which is a transfer arm for transferring the wafer W to the carrier C loaded on 11, is provided. The transfer mechanism 12 is configured so that the holding portion of the wafer W can advance and retreat, can move in the X direction, can rotate around the vertical axis, and can be raised and lowered.

The relay block S2 has the role of transferring the wafer W taken out from the carrier C in the carrier block S1 to the processing block S3. The relay block S2 is a transfer shelf 13 with a plurality of stacks for the wafer W disposed above and below, and a movable load that can be raised and lowered for moving and loading the wafer W between the stacks of the transfer shelves 13. It is provided with a mechanism (14). The transfer shelf 13 has a height position at which the main transfer mechanisms 15a and 15b provided in the processing block S3 can transfer the wafer W, and a height position at which the transfer mechanism 42 can transfer the wafer W. A loading table for the wafer W is arranged at a height that can be reached.

Processing block S3 is a two-story building with processing blocks B1 and B2 stacked on top and bottom. Processing blocks B1 and B2 are structured roughly similarly, and will be explained using processing block B1 as an example. Each processing block B1 is provided with a main conveyance mechanism 15a that is movable along a conveyance path 16 made of, for example, a guide rail, extending in the front-back direction (Y direction) when viewed from the relay block S2. In the processing block B1, modules for processing the wafer W are arranged on both left and right sides of the transfer path 16. In the processing block B1, for example, an application module 2 for applying the coating liquid is provided on the right side as seen from the loading/unloading block S1. Also, on the left side, for example, a solvent volatilization module 3, a reflow module 4, an ultraviolet irradiation module 5, and two cure modules 6 are arranged in an array from the relay block S2 side.

Additionally, the insulating film forming apparatus is provided with a control unit 9 made of, for example, a computer. The control unit 9 has a program storage unit, and in the program storage unit, a program containing instructions to carry out the transfer of the wafer W in the film deposition apparatus or the processing sequence of the wafer W in each module. This is saved. This program is stored in a storage medium such as a flexible disk, compact disk, hard disk, MO (magneto-optical disk), or memory card, and is installed in the control unit 8.

To briefly explain the flow of the wafer W in the insulating film deposition apparatus, when the carrier C containing the wafer W is loaded on the stage 11, the transfer mechanism 12 and the transfer shelf 13 and conveyed to processing block B1 or B2 through the mobile mounting mechanism 14. After that, the coating film 101 is applied to the wafer W in the coating module 2, and the following process occurs: solvent volatilization module 3 → reflow module 4 → ultraviolet irradiation module 5 → cure module 6. are conveyed in order to form an insulating film. Thereafter, the wafer W is transferred to the transfer shelf 13 and returned to the carrier C by the moving mounting mechanism 14 and the transfer mechanism 12.

Additionally, the insulating film forming device may be provided with a polishing device that performs CMP. For example, a polishing device may be provided in place of one cure module 6. Additionally, the wafer W after performing the cure process in the cure module 6 may be polished by CMP.

Next, the application module 2 will be described. The coating module 2 applies, for example, a coating liquid obtained by dissolving polysilazane, which serves as a precursor of an insulating film, in an organic solvent to the wafer W on which the pattern is formed, using a known spin coating method. As shown in FIG. 13 , the coating module 2 is provided with a spin chuck 21 configured to adsorb and hold the wafer W and to be rotatable and capable of being raised and lowered by a drive mechanism 22 . Additionally, reference numeral 23 in FIG. 13 denotes a cup module. Reference numeral 24 in FIG. 13 is a guide member in which the outer circumferential wall and the inner circumferential wall extending downward are formed in a cylindrical shape.

Additionally, a discharge space is formed between the outer cup 25 and the outer peripheral wall, and the lower part of the discharge space has a structure capable of separating gas and liquid. Around the guide member 24, there is provided a liquid receiving portion 27 that begins to extend from the top of the outer cup 25 toward the center and collects the liquid centrifugally removed from the wafer W. In addition, the coating unit 2 is provided with a coating liquid nozzle 28, and, for example, applies a coating liquid such as polysilazane to the wafer W from a coating liquid supply source 29 stored therethrough through the coating liquid nozzle 28. While supplying the coating liquid to the center, the wafer W is rotated at a predetermined number of rotations around the vertical axis to extend the coating liquid on the surface of the wafer W to form a coating film.

Next, the solvent volatilization module 3 will be described. As shown in FIG. 14, the solvent volatilization module 3 includes a lower member 31 made of a flat cylindrical body with an open upper surface in a housing not shown, and moves up and down with respect to the lower member 31 to form a processing container. It is provided with a processing container (30) consisting of a cover portion (32) that opens and closes (2). The lower member 32 is supported on the bottom portion 3a of the housing via a support member 41. Additionally, the lower material 31 is provided with a heating plate 33 embedded with a heating mechanism 34 for loading the wafer W and heating it to, for example, 100 to 250°C. On the bottom portion 3a of the housing, a lifting pin 35 is provided for transferring the wafer W through the bottom portion of the lower material 25 and the heating plate 21 to and from the external main transport mechanism 15a. A lifting mechanism 36 is provided to elevate.

The cover part 32 is made of a flat cylindrical body with an open lower surface, and an exhaust port 38 is formed in the central part of the top plate of the cover part 32, and an exhaust pipe 39 is connected to this exhaust port 38. . The downstream end of this exhaust pipe 39 is connected to a common exhaust duct arranged within the factory, assuming that the processing container 30 side is the upstream side.

The cover portion 32 is loaded so as to contact the pin 40 provided on the upper surface of the peripheral wall portion of the lower material 31, and is loaded so that a slight gap is formed between the cover portion 32 and the lower material, so that the wafer (W) Forms a processing space for heating. And, by exhausting air through the exhaust port 38, the atmosphere inside the housing is configured to flow into the processing container through the gap between the cover portion 32 and the lower material 25. In addition, the lid portion 32 has the ability to be raised and lowered between a lowered position when the processing container 2 is closed and a raised position when the wafer W is delivered to the heating plate 21. It is structured so that In this example, the lifting operation of the cover part 22 is performed by driving the lifting mechanism 37 installed on the outer peripheral surface of the cover part 22.

Additionally, the reflow module 4 is configured in almost the same way as the solvent volatilization module 3, except that the wafer W is heated to 200 to 300° C. by the heating mechanism 34.

As shown in FIG. 15, the ultraviolet irradiation module 5, which is an energy supply module, is provided with a housing 50 in the shape of a rectangular parallelepiped that is flat and elongated in the front-back direction, and has a wafer ( A loading and unloading port 51 for loading and unloading W) and a shutter 52 for opening and closing the loading and unloading port 51 are provided.

The inside of the housing 50 is provided with a transfer arm 53 that transfers the wafer W toward the front when viewed from the loading/unloading/outlet 51. The transfer arm 53 is configured as a cooling plate and is configured to cool the wafer W to room temperature (25°C), for example, after the reflow process and before the ultraviolet irradiation treatment. A loading table 54 for the wafer W is disposed on the inner side as seen from the loading/unloading/exiting port 71. Lifting pins 56 and 58 for transferring wafers are provided below the loading table 54 and the transfer arm 53, respectively, and the lifting pins 56 and 58 are provided with lifting mechanisms 57 and 59, respectively. It is configured to be raised and lowered by .

On the upper side of the loading table 54, an ultraviolet lamp 71, such as a xenon lamp that irradiates ultraviolet light with a main wavelength of 172 nm, is installed to irradiate ultraviolet light to the wafer W loaded on the loading table 54. An accommodating lamp room (70) is provided. The lower surface of the lamp chamber 70 is provided with a light transmission window 72 that transmits ultraviolet light with a wavelength of 172 nm emitted from the ultraviolet lamp 71 toward the wafer W. Additionally, on the lower side wall of the lamp chamber 70, a gas supply section 73 and an exhaust port 74 are provided to face each other. An N ₂ gas supply source 75 for supplying N ₂ gas into the housing 50 is connected to the gas supply unit 73 . An exhaust mechanism 77 is connected to the exhaust port 74 through an exhaust pipe 76 .

When irradiating ultraviolet rays to the wafer W loaded on the loading table 54, N ₂ gas is supplied from the gas supply unit 73 and exhaust is performed to reduce the atmosphere of the wafer W to, for example, 400 ppm or less. More preferably, it is configured to be a low oxygen atmosphere of 50 ppm or less, for example, an N ₂ gas atmosphere. When the wafer W cooled to room temperature on the transfer arm 53 is loaded on the loading table 54, N ₂ gas is supplied from the N ₂ gas supply source 75, and the wafer W is placed in a low-oxygen atmosphere. For example, an energy of 4000mJ/㎠ is irradiated.

Next, the cure module 6 will be described. As shown in FIG. 16, the cure module 6 is configured by providing a processing container 60 composed of a cover portion 62 and a lower member 61 in a housing (not shown). In the processing container 60, a loading table 63 on which wafers W are placed is provided, and the wafers W loaded on the loading table 63 are placed on the loading table 63, for example, from 350 to 450 degrees Celsius. A heating mechanism 65 that heats to ℃ is provided. Additionally, a gas inlet 65 is provided in the top plate portion of the cover portion 62, and one end of a gas supply pipe 66 is connected to the gas inlet 65. The other end of the gas supply pipe 66 is branched into two, and a water vapor source 67 for supplying water vapor into the processing container 60 is connected to one end, and a processing container 60 is connected to the other end. An N ₂ gas supply source 68 for supplying N ₂ gas is connected thereto. In addition, reference numerals V67 and V68 in FIG. 16 denote valves, and M67 and M68 denote flow rate adjustment units.

Additionally, below the gas introduction port 65 in the cover portion 62, a gas diffusion plate 69 is provided so as to face the upper surface of the loading table 63. The gas diffusion plate 69 is composed of, for example, a punching plate, and diffuses the gas introduced into the processing container 60 from the gas inlet 65, toward the wafer W loaded on the loading table 63. supply. Additionally, an exhaust port 82 is formed in the lower member 61, and one end of the exhaust pipe 83 is connected to the exhaust port, and the other end of the exhaust pipe 83 is connected to the exhaust portion.

The cover portion 62 is configured to be raised and lowered by a lifting mechanism 81 installed on the bottom of the housing, and the wafer W is loaded into the processing container 60 with the cover portion 62 raised and placed on the loading table. It is loaded in (63). Then, by lowering the cover 62, the processing container 60 is sealed, and a processing space is formed for supplying water vapor while heating the wafer W loaded on the loading table 63.

As already explained, when the wafer W that has undergone the ultraviolet irradiation treatment is placed on the loading table 63, the processing vessel 60 is filled with water vapor and the wafer W is heated at 400° C. for 30 minutes and 450° C. for 120° C. After heating in stages, the supply of water vapor is stopped and heating is performed at 450°C for 30 minutes in a nitrogen gas atmosphere.

According to the above-described embodiment, the coating liquid containing polysilazane is applied to the wafer W, and after volatilizing the solvent in the coating film 101, before performing the cure process, the coating film ( 101) is being irradiated with ultraviolet rays. For this reason, unbonded hands are likely to be generated at hydrolyzed sites in polysilazane. Therefore, the efficiency of generating hydroxyl groups increases in that unbonded hands are created in silicon, which is a site that is hydrolyzed in advance. In other words, since the energy required for hydrolysis is reduced, even when the temperature of the cure process is set to 350°C, the remaining portions that are not hydrolyzed decrease. As a result, dehydration condensation occurs efficiently, and the crosslinking rate is improved, making it possible to form a dense (high-quality) insulating film.

In addition, the present invention is provided with a film forming apparatus that performs the process from the coating process to the ultraviolet irradiation process, and a heat treatment apparatus that separately performs the curing process, and the wafer W that has been irradiated with ultraviolet rays in the film forming apparatus is transported to the heat treatment apparatus and cured. It may be a substrate processing system that performs processing. As shown in FIG. 17 , the substrate processing system includes a substrate processing device 90 configured in the same manner as the insulating film forming device shown in FIGS. 11 and 12 except that a cure processing device is not provided, and a wafer W. A transport vehicle is provided with a heat treatment apparatus 93 including a heat treatment furnace 97 for performing heat treatment, and is a container transport mechanism that transports the carrier C between the substrate processing apparatus 90 and the heat treatment apparatus 93. (AVG)(98) is provided. The heat treatment device 93 includes a carrier block S1 on which the carrier C is transported, a transfer mechanism 94 for taking out the wafer from the carrier C, and a loading shelf for loading the wafer W taken out from the carrier C. It is provided with 96 and a transfer mechanism 95 that moves and mounts the wafer W loaded on the loading shelf 96 to the heat treatment furnace 97. As the heat treatment furnace 97, for example, a known heat treatment furnace is used, and a plurality of substrates are arranged in a shelf-like manner on a substrate holding tool, placed in a vertical reaction tube surrounded by heaters, and heat treatment (cure) is performed. .

This substrate processing system includes a control unit 91 of the substrate processing device 90, and a heat treatment device 93 having a program for executing the transfer and cure processing processes of the wafer W in the heat treatment device 93. It is provided with a higher-level computer 99 that transmits a control signal to the control unit 92 of ) and controls the transport of the carrier C by the transport vehicle 98. The upper computer 99 stores a program for executing the previously described insulating film forming method, and processes from application of the coating liquid to the wafer W to ultraviolet irradiation treatment are performed in the substrate processing apparatus 90, The wafer W irradiated with ultraviolet rays is stored in the carrier C and transported to the heat treatment device 93 by the transport vehicle 98, where curing treatment is performed. The same method of forming an insulating film can be applied to such a substrate processing system. In this way, it is possible to form a high-strength insulating film even when using a substrate processing system including a heat treatment furnace. On the other hand, since the temperature of the curing process can be lowered, there is also the effect that there is no need for a substrate processing system including a dedicated heat treatment furnace for high temperature treatment when performing the insulating film forming process.

Additionally, in the above-described embodiment, in the cure process, the cure treatment may be performed by heating while supplying ammonia gas. Alternatively, the gas supplied during the cure treatment may be N ₂ gas.

Additionally, the present invention may be applied to the film formation of an interlayer insulating film such as a low dielectric constant film. When forming an interlayer insulating film, the heating temperature is required to be 450°C or lower, for example, 400°C or lower in order to suppress migration and diffusion of copper, which is a wiring material. Additionally, from the viewpoint of forming the interlayer insulating film with sufficient hardness, it is preferable that the temperature is 300°C or higher. The present invention can be expected to be applied to the formation of interlayer insulating films because an insulating film of good quality can be obtained even if the cure temperature is low. Additionally, for example, it may be applied to PMD (Pre Metal Dielectric) as an example of forming an insulating film on a substrate with narrow grooves formed.

Additionally, in the present invention, the insulating film may be formed by applying the coating liquid multiple times. For example, in the insulating film forming apparatus shown in FIGS. 11 and 12, the wafer W on which the trench 110 is formed is first transported to the application module 2, and the first application of the coating liquid is performed. As a result, for example, as shown in FIG. 18, the coating film 101a with the coating liquid entering the inside of the trench 110 formed in the silicon film 100 is formed. 18 to 23, the coating film formed by applying the first coating liquid is indicated by reference numeral 101a, and the coating film formed by applying the second coating liquid is indicated by 101b.

Thereafter, the wafer W is transported to the solvent volatilization module 3 as in the embodiment, the solvent is volatilized, and then transported to, for example, the ultraviolet irradiation module 5, and placed in a low-oxygen atmosphere as shown in FIG. 19. UV rays are irradiated onto the coating film 101a. Next, the wafer W is transported to the coating module 2, and a second coating process is performed. As a result, as shown in FIG. 20, a coating film 101b is additionally laminated on the wafer W. Thereafter, the wafer W is transported to the solvent volatilization module 3, the solvent is volatilized, and then transported to the ultraviolet irradiation module 5, and ultraviolet rays are applied to the coating film 101b in a low-oxygen atmosphere as shown in FIG. 21. investigate. Subsequently, the wafer W is transferred to the cure module 6, and as shown in FIG. 22, it is heated in stages at 400°C, 450°C under a water vapor atmosphere, and then heated to 450°C under an N ₂ gas atmosphere. . Thereafter, for example, the wafer W is transported to a CMP device, and the surface coating film 101b is removed by CMP, as shown in FIG. 23.

When ultraviolet rays are irradiated on the coating films 101a and 101b, the ultraviolet rays penetrate from the surface side of the coating films 101a and 101b to the lower layer side, so the lower layer side of the coating films 101a and 101b receives more ultraviolet rays than the surface layer side. This tends to be weak, and there is a risk that the Si-H bond may not become sufficiently unbonded. Therefore, when the wafer W is cured, the crosslinking rate may be lowered on the lower layer side of the coating films 101a and 101b, and the crosslinking rate as a whole film may be lowered. Additionally, for example, when the surface coating film is removed by CMP, there is a risk that a layer of poor film quality in the coating film may be exposed.

Therefore, the application of the coating films 101a and 101b and the irradiation with ultraviolet rays are repeated multiple times to form the coating films 101a and 101b with a predetermined film thickness, so that the coating films 101a and 101b are irradiated with ultraviolet rays while each is thin. Processing is possible, and unbonded losses are easily formed in the entire layer of the coating films 101a and 101b. Therefore, when the cure treatment is performed, crosslinks are easily formed in all layers of the coating films 101a and 101b, and dense coating films 101a and 101b with a high crosslinking rate over all layers can be formed. As a result, as shown in Example 2 described later, an insulating film that is more dense and has a higher etching strength can be formed.

Additionally, after performing the first coating treatment, volatilizing the solvent, and irradiating ultraviolet rays to the coating film 101a in a low-oxygen atmosphere, it may be further transferred to the cure module 6 and heated at, for example, 350° C. in a water vapor atmosphere. . Thereafter, a second coating treatment may be performed, and after volatilizing the solvent, the coating film 101b may be irradiated with ultraviolet rays in a low-oxygen atmosphere and further cured.

Additionally, after volatilizing the solvent in the first coating process and the second coating process, a reflow process of heating the wafer W at 250° C., for example, may be performed.

Additionally, the present invention may be applied to, for example, a process of forming a sacrificial film. Figure 24 shows an example of a substrate to be processed on which a sacrificial film has been formed. As shown in FIG. 24, the wafer W has a polysilicon layer 103 formed on the upper surface of the SiO ₂ film 102, and a trench 110 is formed to penetrate the polysilicon layer 103 in the thickness direction. It is formed. Then, a SiON film 104 serving as a sacrificial film is formed on the upper surface of the wafer W. FIG. 24 shows a cross-section of the surface layer portion of the wafer W after forming the SiON film 104 and etching the SiON film 104 in a predetermined pattern. In this wafer W, using the etching selectivity of the SiO ₂ layer 102 relative to the SiON film 104 and the polysilicon layer 103, the SiON film 104 is not covered with the SiON film 104. ) is etched away from the SiO ₂ layer 102 facing the bottom of the removed trench 110 .

The sacrificial film, such as the SiON film 104, preferably has good embedding properties in that it is deposited on the wafer W on which irregularities such as a circuit pattern are formed. Therefore, it is preferable to form a film by applying a coating liquid. In addition, it is desirable that the etching intensity be high in order to sufficiently increase the etching selectivity with the film to be etched, here, the SiO ₂ film 102.

When forming the SiON film 104, for example, a coating liquid containing polysilazane as a precursor is applied toward the wafer W. Then, as shown in FIGS. 3 to 6, the coating film 101 is heated at, for example, 150°C for 3 minutes to volatilize the solvent in the coating film 101, and then heated at 250°C to form the coating film 101. ) reflow. Next, the coating film 101 is irradiated with ultraviolet rays of 5000 J/cm 2 or less under a low-oxygen atmosphere. Thereafter, in the cure module 6, a cure process is performed in which the wafer W is gradually heated at 400°C and 450°C in an N ₂ gas atmosphere.

In the polysilazane contained as a precursor, when dehydration condensation of the oligomers contained in the coating film 101 proceeds as described above, -Si(NH)Si- contained in the polysilazane becomes Si-O- It is replaced by a Si bond. If the substitution rate from -Si(NH)Si- to Si-O-Si bonds is high, it approaches SiO ₂ , and by forming the film so that more -Si(NH)Si- remains, it becomes a SiON film with a high N concentration. Therefore, after irradiating the coating film 101 with ultraviolet rays, it is heated to 350°C in a cure process, for example, in an N ₂ gas atmosphere. At this time, by performing a cure treatment at a low temperature, for example, 350 to 450°C, substitution of -Si(NH)Si- is suppressed, and unbonded hands formed by irradiation of ultraviolet rays are, as already explained, Hydrolysis and dehydration condensation are performed to produce Si-O-Si bonds. Therefore, by crosslinking the oligomer of polysilazane, a strong film is formed, and the escape of nitrogen is suppressed, making it possible to form a SiON film with a high nitrogen content.

Additionally, in the process of irradiating ultraviolet rays, if the temperature at which crosslinking occurs, for example, in polysilazanes, is raised to 350 to 400°C, the formation of unbonded hands, hydrolysis, and dehydration condensation may proceed simultaneously. Therefore, isolated oligomers are trapped within the bound oligomers, and as a result, the density of the insulating film decreases.

Therefore, the temperature at which ultraviolet rays are irradiated is preferably 350°C or lower. In addition, since it is a requirement that the temperature is such that crosslinking does not proceed when irradiated with ultraviolet rays, ultraviolet rays may be irradiated in the reflow process. However, in the solvent volatilization process, there is a risk that the solvent, which is a solvent, may deteriorate due to irradiation of ultraviolet rays. Therefore, it needs to be done after the solvent volatilization process.

Additionally, if the energy in the energy irradiation process is too large, bonds other than the Si-H bond may be cleaved. Therefore, the energy irradiation amount is preferably 5000 J/cm2 or less, and any irradiation amount greater than the dose sufficient to break the terminal of the Si-H bond is sufficient.

Additionally, as shown in Example 3 described later, the effect can be increased by performing the above-described insulating film forming method while setting the heating temperature of the wafer W in the solvent volatilization process to 200 to 250°C. This is because the energy absorbed by the solvent decreases by more reliably removing the solvent in the coating film 101, and in Example 3, reflow processing is not performed, and this corresponds to rearrangement of oligomers in the reflow processing. It is presumed that this is a synergistic effect because the effect of

Also, from the viewpoint of efficiently forming unbonded hands, the energy of a wavelength that is absorbed by the coating film without transmitting through the coating film is preferable. Therefore, in the case of ultraviolet rays, it is preferable that the main wavelength is 200 nm or less. For example, ultraviolet rays with a wavelength of 193 nm, such as an ArF lamp, may be used, or a deuterium lamp, etc. may be used. Additionally, an electron beam or the like may be used as the energy to irradiate the coating film.

Additionally, a device for volatilizing the solvent in the coating film 101 used in the solvent volatilization process may, for example, reduce the pressure inside the sealed processing container to, for example, half of atmospheric pressure, and A device that promotes volatilization of the solvent and volatilizes the solvent may be used.

<Example>

<Evaluation Test 1>

The following test was conducted to verify the effect of the embodiment of the present invention. Using the substrate processing system shown in FIG. 17, an insulating film was formed on the evaluation wafer W, and the etching strength of the insulating film was evaluated.

[Example 1]

In the ultraviolet ray irradiation process in the insulating film formation method, an example in which ultraviolet rays with a main wavelength of 172 nm were irradiated under an N ₂ gas atmosphere so that the dose was 2000 mJ/cm 2 was referred to as Example 1-1. In addition, after applying the coating liquid shown in the embodiment, the wafer W is heated at 150° C. for 3 minutes in a solvent volatilization process, and then subjected to an ultraviolet irradiation process without performing a reflow process. It was done. In the subsequent cure process, two stages of heating were performed in a heat treatment furnace, with water vapor supplied, at 400°C for 30 minutes and at 450°C for 120 minutes, and then heated at 450°C for 30 minutes in an N ₂ gas atmosphere. . Additionally, the target film thickness of the coating film was 100 nm.

[Comparative Examples 1, 2]

In addition, in the ultraviolet irradiation process, an example treated in the same manner as Example 1-1 was referred to as Comparative Example 1, except that 2000 mJ/cm2 ultraviolet rays were irradiated in an air atmosphere. Additionally, an example treated in the same manner as Example 1-1, except that ultraviolet irradiation was not performed, was referred to as Comparative Example 2.

In each of Example 1 and Comparative Examples 1 and 2, wet etching was performed with 0.5% dilute hydrofluoric acid to evaluate the etching amount (etching rate) per unit time, and the etching rate of the thermal oxidation film of silicon with respect to 0.5% dilute hydrofluoric acid was The relative etching rate in each example when set to 1 was determined. In the following examples, the etching strength was evaluated based on this relative etching rate.

The relative etching rates in Comparative Examples 1 and 2 were 3.74 and 5.55, respectively. In comparison, the relative etching rate in Example 1 was 2.04.

According to these results, when forming an insulating film by applying a coating solution containing polysilazane to the wafer W, the etching strength can be increased by irradiating the energy of ultraviolet rays under an N ₂ gas atmosphere to the coating film before the cure process. It can be said that there is.

In addition, in each of Example 1 and Comparative Example 1, (FT-IR: Fourier transform infrared spectrophotometer) was used to evaluate the amount of atomic bonding before and after ultraviolet irradiation treatment and after curing treatment. In Comparative Example 1, after ultraviolet irradiation treatment, Si-H bonds decreased and Si-O bonds increased. Additionally, in Example 1, a decrease in the Si-H bond was observed after the ultraviolet irradiation treatment, but the Si-O bond did not increase, and the Si-O bond increased after the curing treatment.

Inferring from this result, by performing ultraviolet irradiation treatment, Si-H bonds can be reduced and unbonded hands can be formed. However, if ultraviolet irradiation treatment is performed in an air atmosphere, the crosslinking reaction proceeds before curing treatment, and ultraviolet irradiation treatment is performed. It is thought that if the treatment is performed in an N ₂ gas atmosphere, the crosslinking reaction before the cure treatment can be suppressed. It is assumed that the etching strength is increased by forming unbonded hands and suppressing the crosslinking reaction before the cure treatment.

In addition, when the ultraviolet ray dose was set to 3000 and 4000 mJ/cm2, the relative etching rates were evaluated and were 2.70 and 2.42, respectively, and an insulating film with high strength was obtained even at a ultraviolet ray dose of about 4000 mJ/cm2.

<Evaluation Test 2>

In addition, in order to verify the effect of repeating the application of the coating liquid to the wafer W and the ultraviolet ray irradiation treatment on the coating film multiple times, and then performing the curing treatment, the substrate shown in FIG. 17 was prepared according to the following examples. Using the processing system, an insulating film was formed on the wafer W, the relative etching rate was determined in the same manner as in Example 1, and the etching strength of the insulating film was evaluated.

[Example 2-1]

After applying the first coating liquid to the evaluation wafer W, in the solvent volatilization process, the wafer W was heated at 150°C for 3 minutes, and then, without performing a reflow process, ultraviolet ray irradiation was performed as in the embodiment. The process was carried out. In the ultraviolet irradiation process, the dose of ultraviolet light with a wavelength of 172 nm irradiated under N ₂ gas atmosphere was set to 4000 mJ/cm2. In addition, as the second application of the coating liquid, after applying the same amount of coating liquid as the first coating liquid, in the solvent volatilization process, the wafer W is heated at 150°C for 3 minutes, and then the reflow process is not performed. , the ultraviolet irradiation process was performed similarly to the embodiment. Thereafter, an example in which the same cure process as Example 1 was performed was designated as Example 2-1. In addition, the supply amount of the coating liquid for the first application of the coating liquid and the second application of the coating liquid was approximately the same as in Example 1, and the target film thickness of the coating film after curing was set to 200 nm.

[Example 2-2]

The application amount of the coating liquid was approximately twice that of Example 1, the target film thickness of the coating film was formed at 200 nm, and the dose of ultraviolet rays with a wavelength of 172 nm irradiated in an N ₂ gas atmosphere in the ultraviolet ray irradiation process was 4000 mJ. An example treated in the same manner as Example 1, except that it was set to /cm2, was designated as Example 2-2.

The relative etching rates in Examples 2-1 and 2-2 were 2.27 and 2.56, respectively. In both Examples 2-1 and 2-2, it can be seen that the relative etching rate is low and the etching intensity is high. Additionally, compared to Example 2-2, it can be seen that Example 2-1 has a lower relative etching rate.

According to these results, it can be said that a denser and better insulating film can be obtained by repeating the application of the coating liquid to the wafer W and the ultraviolet irradiation treatment to the coating film multiple times.

<Evaluation Test 3>

Additionally, in order to verify the effect of the heating temperature of the wafer W in the solvent volatilization process, an insulating film was formed on the wafer W using the substrate processing system shown in FIG. 17 according to the following example, The etching strength of the insulating film was evaluated.

[Example 3-1]

After applying the coating liquid shown in the embodiment to the wafer W, in the solvent volatilization process, the wafer W is heated at 150° C. for 3 minutes and then subjected to an ultraviolet ray irradiation process without performing a reflow process. did. In the subsequent cure process, two stages of heating were performed in a heat treatment furnace, with water vapor supplied, at 400°C for 30 minutes and at 450°C for 120 minutes, and then heated at 450°C for 30 minutes in an N ₂ gas atmosphere. . Additionally, the target film thickness of the coating film was 100 nm.

[Example 3-2, 3-3]

Examples treated in the same manner as Example 3-1, except that the heating temperature of the wafer W in the solvent volatilization process was set to 200°C and 250°C, were referred to as Examples 3-2 and 3-3, respectively.

The relative etching rates in Examples 3-1, 3-2, and 3-3 were 3.68, 2.74, and 2.74, respectively. It can be said that a denser and better insulating film can be obtained by increasing the heating temperature of the wafer W in the solvent volatilization process.

2: Applicator module
3: Solvent volatilization module
4: Reflow module
5: Ultraviolet irradiation module
6: Cure module
9, 90, 92: Control unit
99: Parent computer
100: Silicone film
101: coating film
W: wafer

Claims (16)

In the method of forming an insulating film in the groove of shallow trench isolation,
A process of forming a coating film by applying a coating liquid obtained by dissolving a precursor for forming an insulating film containing silicon oxide in a solvent to a substrate;
A solvent volatilization step of volatilizing the solvent in the coating film,
After this process, an energy supply process of supplying energy to the coating film in a low-oxygen atmosphere with a lower oxygen concentration than the atmosphere in order to generate unbonded losses in the molecular groups constituting the precursor;
Thereafter, a method of forming an insulating film comprising a cure process of heating the substrate and crosslinking the precursor to form an insulating film. According to paragraph 1,
A method of forming an insulating film, characterized in that, after the process of volatilizing the solvent, a reflow process of heating the substrate to rearrange the molecular groups in the coating film is performed. According to paragraph 2,
A method of forming an insulating film, characterized in that the energy supply process is performed with the temperature of the substrate lowered after the reflow process. According to paragraph 1,
A method of forming an insulating film, characterized in that the hypoxic atmosphere in which the energy supply process is performed has an oxygen concentration of 400 ppm or less. According to paragraph 1,
A method of forming an insulating film, wherein the low oxygen atmosphere is an atmosphere containing an inert gas. According to paragraph 1,
A method of forming an insulating film, characterized in that the energy is the energy of ultraviolet rays whose main wavelength is shorter than 200 nm. According to clause 6,
A method of forming an insulating film, characterized in that the energy of ultraviolet rays supplied to the coating film is 5000 mJ/cm2 or less. According to paragraph 1,
A method of forming an insulating film, characterized in that the process group from the process of forming the coating film to the process of supplying the energy is repeated multiple times, and then the cure process is performed. According to paragraph 1,
The cure process is a method of forming an insulating film, characterized in that the substrate is heated in a water vapor atmosphere. According to paragraph 1,
A method of forming an insulating film, characterized in that the heating temperature of the substrate in the cure process is 300°C or more and 450°C or less. In the film forming apparatus for forming an insulating film in the groove of the shallow trench isolation on a semiconductor wafer, which is a substrate,
a coating module for forming a coating film by applying a coating liquid obtained by dissolving a precursor for forming an insulating film containing silicon oxide in a solvent to a substrate;
A solvent volatilization module for volatilizing the solvent in the coating film,
In order to activate the precursor, an energy supply module for supplying energy to the coating film in which the solvent has been volatilized in a low-oxygen atmosphere with a lower oxygen concentration than the atmosphere;
a cure module for heating the substrate processed in the energy supply module and crosslinking the precursor to form an insulating film;
An insulating film deposition device comprising a substrate transport mechanism for transporting a substrate between each module. According to clause 11,
An insulating film forming device, characterized in that the solvent volatilization module is a heating module for heating a solvent that heats a substrate. According to clause 11,
An insulating film forming device comprising a heating module for reflow that heats the substrate to rearrange the molecular groups in the coating film from which the solvent has been volatilized. According to clause 11,
An insulating film forming device, wherein the energy supply module is a module for irradiating ultraviolet rays with a main wavelength shorter than 200 nm to the coating film. According to clause 11,
The cure module is an insulating film deposition device characterized in that the substrate is heated by supplying water vapor to the substrate. In the substrate processing system for forming an insulating film in the groove of the shallow trench isolation on the semiconductor wafer,
A loading/unloading port for loading and unloading a substrate into a transfer container, a coating module for forming a coating film by applying a coating liquid obtained by dissolving a precursor for forming an insulating film containing silicon oxide in a solvent to the substrate, and a coating module within the coating film. A solvent volatilization module for volatilizing the solvent, an energy supply module for supplying energy to the coating film in which the solvent has been volatilized in a hypoxic atmosphere with a lower oxygen concentration than the atmosphere to activate the precursor, and each module and the carrying-in A substrate processing device provided with a substrate transport mechanism for transporting substrates between output ports,
a cure device for heating the substrate processed in the energy supply module and crosslinking the precursor to form an insulating film;
A substrate processing system comprising a container transport mechanism for transporting the transport container between the loading/unloading port of the substrate processing apparatus and the cure device.

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